Resin oil modified resoles

ABSTRACT

THE INVENTION RELATES TO RESOLE RESINS PRODUCED BY REACTING UNDER BASIC AQUEOUS CONDITIONS FORMALDEHYDE WITH A PHENOL WHICH HAS BEEN PREVIOUSLY PREPARED BY PARTIAL ALKYLATION OF PHENOL WITH A SPECIFIC MIXTURE OF CARBOCYCLIC COMPOUNDS CONTAINING BETWEEN 8 TO 13 CARBON ATOMS. THE RESOLE RESIN HAS UTILITY IN THE MANUFACTURE OF IMPREGNATED SHEETS, LAMINATES, AND OTHER REINFORCED PLASTICS.

United States Patent O 3,761,448 RESIN OIL MODIFIED RESOLES George J.Anderson, Indian Orchard, and Ronald H.

Dahms, Springfield, Mass., assignors to Monsanto Company, St. Louis, M0.

N Drawing. Continuation-impart of applications Ser. No. 588,310, Oct.21, 1966, Ser. No. 676,043, Oct. 18, 1967, Ser. No. 738,812, June 21,1968, all now abandoned, and Ser. No. 122,525, Mar. 9, 1971, now PatentNo. 3,691,121. This application Aug. 1, 1972, Ser. No. 276,944

Int. Cl. C08g 37/10, 51/34; C09v /08 US. Cl. 260-53 R 6 Claims ABSTRACTOF THE DISCLOSURE The invention relates to resole resins produced byreacting under basic aqueous conditions formaldehyde with a phenol whichhas been previously prepared by partial alkylation of phenol with aspecific mixture of carbocyclic compounds containing between '8 and 13carbon atoms. The resole resin has utility in the manufacture ofimpregnated sheets, laminates, and other reinforced plastics.

RELATED APPLICATIONS This application is a continuation-in-part of ourearlier filed US. patent applications, Ser. No. 588,310, filed Oct. 21,1966, Ser. No. 676,043, filed Oct. 18, 1967, Ser. No. 738,812, filedJune 21, 1968, all now abandoned, and Ser. No. 122,525, filed Mar. 9,1971, now US. Patent 3,691,121.

BACKGROUND OF THE INVENTION Phenolic varnishes using phenol-aldehyderesole type resins have long been used to impregnate cellulosic andother woven and nonwoven materials, especially in fibrous sheet form,and to prepare laminates thereof. However, resole resins heretoforeknown when cured have generally suifered from a lack of properties forcertain applications, for example, electrical properties, waterresistance properties, and mechanical strength properties. Because ofthese deficiencies, there has been a long felt need in the art of resoleresins for modified phenol-aldehyde resole resins which would overcomeone or more of these deficiencies.

One approach to producing modified phenol-aldehyde resins has involvedusing as starting materials for reaction with aldehydes substitutedphenols so as to produce phenol-aldehyde resins having a high molecularweight in proportion to the total amount of phenol used in resinmanufacture. The ratio of resole resin prepolymer molecular weight(before curing) to starting phenol content can be termed, forconvenience purposes, the PMW efficiency.

In the past, increases in PMW efficiency have been attempted either byusing naturally occurring substituted phenols, for example, cresol orcresylic acid, or by using synthetically substituted phenols includingnaturally occurring drying oils (such as tung oil or oiticica oil),terpenes, and various unsaturated hydrocarbon materials (such asstyrene) Phenol-aldehyde resins made from phenols substituted with thesestarting materials, however, have a plurality of disadvantages. For onething, the cost of starting materials is so significant that the cost ofthe resulting phenol-aldehyde resin is increased to the point where itis not competitive with other polymeric materials as respects many useapplications. In addition, the resulting phenol-aldehyde product whencured either has an undesirably wide distribution of physical andchemical properties (perhaps caused by using a substituted phenolmixture in which the substituents vary widely from one 3,761,448Patented Sept. 25, 1973 ice another structurally), or has an undesirablynarrow distribution of physical and chemical properties (perhaps causedby using a substituted phenol in which the substituents vary onlyslightly or even not at all from one another structurally). Furthermore,even though the PMW efliciency is improved by using such prior artsubstituted phenols, the phenolic product resole resins derivedtherefrom tend to be inferior as respects such properties as storagestability, viscosity, cure rate, or necessity for close manufacturingtolerances.

It has now been discovered that when one reacts an aldehyde with aphenol which has been synthetically substituted with a certainwell-defined mixture of C to C carbocyclic compounds, there is produceda phenol-aldehyde resole resin product which has a high PMW etficiency.When such resole resin product is used as the resin component in avarnish, the resulting novel varnish has the capacity, when used in themanufacture of laminates, to produce when thermoset, an excellentcombination of electrical, mechanical, and Water resistance properties.These varnishes can contain resin solids which are advanceable to agreater extent without forming precipitates from the varnish organicsolvent phase than is the case with aqueous solutions of these newphenol-aldehyde resole resin products.

When such substituted phenol-aldehyde (especially one usingformaldehyde) resole resin is made into a varnish, such varnish has goodstorage stability and low viscosity characteristics--propertiesdesirable in phenolic varnishes intended for use in laminatemanufacture. Thus, resulting varnishes are useful for impregnating apreformed integral sheet of fibrous cellulosic material, such as cloth,paper, asbestos, and the like, and for making laminates thereof. Theseend products have generally improved properties heretofore unknown. Forexample, such a product laminate gives surprisingly and unexpectedly acombination of better electrical, mechanical, water absorptionproperties than known prior art laminates. Such resole resinsthemselves, when thermoset, characteristically have surprisingly lowerglass transition temperatures than resole resins made, say, from analdehyde and a substituted phenol, such as cresol.

SUMMARY This invention is directed to certain phenol-aldehyde resoleresins. These resole resins in organic solvents form varnishes which areespecially adapted for use in the manufacture of impregnated sheetmaterials and of laminates thereof. The products have high flexuralstrength, low water absorption and excellent electrical properties.These varnishes display excellent penetration qualities as respectsnonwoven, sheet-like materials.

The varnishes prepared from the resole resins of this inventioncomprise:

(A) From about 20 to weight percent of a dissolved mixture of aphenol-formaldehyde resole resin;

(B) From about 0.5 to 15 weight percent of dissolved water;

(C) The balance up to weight percent of any given varnish being anorganic liquid which:

(1) is substantially inert (as respects such resin and water,

(2) evaporates below about C. at atmospheric pressures,

(3) is a mutual solvent for said resole resin and said water (ifpresent), the amount of said organic liquid being present in any givenvarnish being such as to maintain both said resole resin and said waterin dissolved form.

The phenol-formaldehyde resole resin of this invention has aformaldehyde to phenol mol ratio of from about 0.8 to 2.0 (preferablyfrom about 0.9 to 1.5), and is produced by reacting, in the presence ofa basic organic catalyst under liquid aqueous phase conditions, acertain sub stituted phenol mixture with formaldehyde. The resole resinused in this invention further has a relatively high molecular weight asshown by the fact that it is substantially water-insoluble, but it alsohas a methanol solubility such that a 60 weight percent solution thereofcan be prepared in methanol.

Such methanol solution characteristically has a viscosity not greaterthan about 5000 centipoises, and preferably this viscosity lies in therange from about 50 to 500 centipoises. In addition, this resin has afree formaldehyde content which is less than about 5 weight percent(based on total dry resin weight).

The substituted phenol mixture used to make such resin is prepared byreacting phenol under Friedel-Crafts conditions with a controlledmixture of carbocyclic compounds. The mixture of carbocyclic compoundscomprises (on a 100 weight percent basis when in a form substantiallyfree of other materials);

(A) From about 10 through 40 weight percent of compounds each moleculeof which has:

(1) the indene nucleus, (2) from 9 through 13 carbon atoms, (3) asnuclear substituents from through 4 methyl (B) From about 5 through 70weight percent of compounds each molecule of which has:

(1) the dicyclopentadiene nucleus,

(2) from about through 13 carbon atoms,

(3) as nuclear substituents from 0 through 3 methyl groups,

(C) From about through 65 weight percent of compounds each molecule ofwhich has:

(1) a phenyl group substituted by a vinylidene group,

(2) from about 8 through 13 carbon atoms,

(3) as substituents from 0 through 3 groups selected from the classconsisting of methyl and ethyl,

(D) From about 0 through 5 weight percent divinyl benzene;

(E) Provided that the sum total of all such compounds in any given suchmixture of carbocyclic compounds is always 100 weight percent.

At the time when such controlled mixture of carbocyclic compounds isreacted with phenol as indicated, there can be present in such mixtureas diluents inert (i.e. as respects reactivity towards phenol underFriedel- Crafts reaction conditions) organic compounds such as aromaticand aliphatic hydrocarbons. Thus, there is present, conveniently, atleast about 25 weight percent of diluent in such total combination ofmixture of carbocyclic compounds and diluent, although this value isvariable depending upon reactants and reaction conditions. While thereis no apparent upper limit on the amount of diluent present, it ispreferred that the amount of diluent present be not greater than about95 weight percent (same basis). Preferably, the amount of diluent rangesfrom about 15 to 70 weight percent (same basis). Up to about 10 weightpercent (same basis) of water can be present, but it is preferred to usesubstantially anhydrous conditions.

Carbocyclic compound mixtures useful in this invention are availablecommercially from various petroleum producers under a variety of tradenames. For example, one suitable carbocyclic compound mixture isavailable from Enjay Chemical Company under the trade designation HeartCut LPD. Another suitable such mixture is available from MonsantoCompany, St. Louis, Mo., under the trade designation Resin Oil. Stillanother such mixture is available from Gulf Oil Company under the tradedesignation Resin Former Feed Stock. A presently preferred such mixtureis the Monsanto Company Resin Oil which is a C to C product cut with aTABLE I Gulf oil Monsanto 3 Eujay 4 Carbocyclic compounds:

vinylidene aromatics:

Divinyl benzene Cm Indenes:

Indene C Methylindene 010.. Cyclopentadienes:

Isoprene-eyelopentadiene Cm. Dicyclopentadiene Cm MethylcyclopentadiencC Dilucnts:

Alkyl aromatics:

Benzene 00.... Toluene C C4 Alkylbenzene Cm Naphthalenes: Naphthalen C14O. 2 Unidentified (aliphatics) 2.1 Total carbocyclic compound mixturecontent 84. 8

ASTM boil range. F. (ASTM Initial boiling point 283 315 307 End point-364 402 411 Res ue 1.0 Specific gravity 0.952 0. 933 0. 909

l This styrene compound is selected from the group consisting of ethylstyrene and dimethylstyrene.

2 Available commercially from the Gulf Oil Company as Resin Former FeedStock.

3 Available commercially from the Monsanto Company under the tradedesignation Resin Oil.

4 Available commercially from Enjay Company under the trade designationHeart Out LPD."

By the term dicyclopentadiene reference is had to a molecule having thestructure:

By the phase when in a form substantially free of other materialsreference is had to a mixture (e.g. of starting materials, of products,or the like, as the case may be) which is substantially free (e.g. on ananalytical or a theoretical basis) of substances (like inserts) otherthan such mixture itself. For example, in Table I above, the carbocycliccompound mixtures are composed of indenes, vinylidene aromatics, anddicyclopentadienes as well as inert diluents, such as alkyl aromatics,naphthalenes and unindentified aliphatics, but each contains acombination (on a weight percent basis in a form substantially free ofother materials) of components (indenes, dicyclopentadiene, andvinylidene aromatics) as described above.

To react phenol with such an aforedescribed carbocyclic compoundmixture, it is convenient to use Friedel- Crafts conditions, asindicated.

The term Friedel-Crafts conditions as used herein refers to theconventional conditions known to those of ordinary skill in the art usedfor the alkylating or arylating of hydrocarbons (including phenol) bythe catalytic action of aluminum chloride or equivalent acid catalyst inthe presence of appropriate heat and pressure. In the practice of thisinvention, the phenol and suitable Friedel- Crafts acid catalyst aremixed, brought to the proper temperature, and the carbocyclic compoundmixture metered into the acidified (or catalyzed) phenol.

For purposes of this invention, the reaction of carbocyclic compoundmixture with phenol is preferably carried out at temperatures in therange of from about 25 to 200 0., although higher and lower temperaturescan be used. Also, the reaction is preferably conducted under liquidphase conditions at or below atmospheric pressure althoughsuperatmospheric pressures can be used. Inert hydrocarbons, as indicatedabove, generally facilitate the process. Such inert hydrocarbons can bereadily removed, such as by vacuum stripping, at the completion of thereaction if desired. Especially when stripping is contemplated, the mostpreferred inert hydrocarbons have boiling points between about 70 and140 C. The progress of the reaction can be monitored, if desired, bymeasuring the quantity remaining of unreacted carbocyclic compoundmixture using, for example, vapor phase chromatography.

Friedel-Crafts catalysts which may be used in place of aluminumchloride, or together with aluminum chloride, include:

(A) Other inorganic halides, such as gallium, titanium, antimony andzinc halides (including ZnCl (B) Inorganic acids such as sulphuric,phosphoric and the hydrogen halides (including HF);

(C) Activated clays, silica gel and alumina;

(D) BF and BE, organic complexes, such as complexes of ER, with organiccompounds, such as ethanol, butanol, glycol, phenol, cresol, anisole,ethyl ether, isopropyl ether, di-n-butyl ether, formic acid, aceticacid, propionic acid and the like, or with inorganic acids, such asphosphoric acid, sulfuric acid, and the like, and

(E) Alkyl, aryl and aralkyl sulfonic acids, such as ethane-sulfonicacid, benzene sulfonic acid, benzene disulfonic acid, chlorobenzenesulfonic acid, 3,4-dichlorobenzene sulfonic acid, cresol sulfonic acids,phenol sulfonic acids, toluene sulfonic acids, xylene sulfonic acids,octylphenol sulfonic acid, fl-naphthalene sulfonic acid,l-naphthol-4-sulfonic acid, and the like.

When BF as such, is employed, it is conveniently fed to a reactionmixture in gaseous form.

While any combination of carbocyclic compound starting mixture, phenol,and catalyst can be used, it is particularly convenient to react phenolwith carbocyclic compound mixture in the presence of less than about 10weight percent (based on the starting phenol) of acid catalyst.Typically, from about 0.1 to 1 weight percent of Friedel-Crafts acidcatalyst is employed (based on phenol).

The reaction mass is heated to a temperature in the range of from about25 to 200 C. The rate of this reaction is dependent, to some degree, onthe temperature employed. In general, the reaction is rapid, and acomplete reaction between phenol and carbocyclic compound mixture ispreferred. Generally, a total heating time of from about 10 minutes to 4hours is employed. The various process variables are summarized in TableII below.

TABLE II Broad range Process variable Temperature 0.)-.-"

Preferred range About 25 to 200 0.... About 40 to 125 0.

1 n a100 weight percent basis when ina form substantially free of othermaterials.

The properties of a given so-substituted phenol product are affected bythe process conditions used to make that product (e.g. molecular weightdistribution, color, and the like). The resulting reaction product is,as those skilled in the art will appreciate, a complex mixture ofvarious different substituted phenols produced from the reaction ofphenol under Friedel-Crafts conditions with the carbocyclic compoundstarting mixture to produce phenol molecules which are substituted bothon ring carbon atoms and on phenol hydroxyl oxygen atoms by moietiesderived from such carbocyclic compound.

A substituted carbocyclic compound phenol product can be prepared in aform substantially free of starting materials by conventionaldistillation separation techniques (e.g. steam distillation, vacuumstripping, and the like), as those skilled in the art will appreciate,but in making resoles for use in this invention, such product can beused directly as made.

In general, to produce a resole for use in this invention, a substitutedphenol product, as just described, is neutralized under aqueous liquidphase conditions as by the addition of base (ammonium hydroxide and/oramine), and then from about 0.8 to 2.0 mols of formaldehyde per one molof phenol (preferably from about 1.0 to 1.5 mols formaldehyde per mol ofphenol) is mixed with the substituted phenol product (now itself astarting material). Water may be added with the formaldehyde. Formalinis preferred as a source for formaldehyde. Also, a basic catalystmaterial, such as ammonium hydroxide and/or amine selected from thegroup consisting of primary amines (such as ethylamine, isobutylamine,ethanol amine, cyclohexylamine, and the like); secondary amines (such asdiethanol amine, piperidine, morpholine, and the like); and tertiaryamines (such as hexamethylene tetrarnine, triethylamine,triethanolamine, diethyl cyclohexyl amine, triisobutyl amine; and thelike) is introduced into the reaction mixture. Preferred amine catalystshave molecular weights below about 300 and more preferably below about200. The amine catalyst may include hydroxyl groups which tend topromote solubility of the amine in the reaction mixture. This basiccatalyst itself thus can be used to neutralize the starting substitutedphenol. The pH of this reaction mixture is maintained from (7.0 andpreferably above about 7.5) but below about 8.5. This reaction mixtureis then heated to temperatures of from about 60 to C. for a timesufficient to substantially react most of the formaldehyde and therebyproduce a desired resole product. Times of from about 20 to minutes aretypical. Aqueous liquid phase preparation conditions are used.

It will be appreciated that the formaldehyde to phenol mol ratios hereindescribed have reference to the total amount of phenol present before areaction, including the phenol which is substituted by the carbocycliccompound mixture, as described above.

To optimize electrical properties in resoles used in this invention, itis preferred to use as a basic catalyst, when reacting such substitutedphenols with formaldehyde to make resole resins, one which is non-ionicand nonmetallic in character.

The resole product produced by reacting the substituted phenol withformaldehyde as described above is one composed of methylolatedsubstituted phenol which has been methylolated by the formaldehyde to adesired methylol content and optionally advanced (e.g. the molecularweight of the methylolated substituted phenol increased) as by heatingas necessary or desirable to make a resole resin product havingmolecular Weight characteristics as above indicated. As those skilled inthe art fully appreciate, the methylol content and the degree ofadvancement are readily controllable, so that one can optimize such aresole resin for use in a particular application. For purposes of thisinvention, a phenol-formaldehyde resole resin or resole can be regardedas being the reaction product of the above-described substituted phenolmixture and formaldehyde under the aqueous base catalyzed conditions asdescribed herein which product can be thermoset by heat alone withoutthe use of a curing catalyst.

In general, such a resole product as made is a brown colored, unstable,multiphase aqueous emulsion whose viscosity depends, in any giveninstance, upon process and reactant variables, but which usually rangesfrom a syrupy liquid to a semi-solid state. Such a resole productusually separates from such aqueous phase as a brown colored materialwhose viscosity varies from a syrup to a solid.

To recover the resole resin of this invention such an emulsion isdehydrated, preferably under heat and reduced pressure, to a watercontent of from about 0.5 to 15 weight percent (based on total resoleweight). When the resulting water content is over about 2 weightpercent, there is produced a single-phased, clear dark-colored, highsolids, resole resin. In any given instance, its total solids content,(residual) water content, and viscosity depend upon the amount ofsubstituted phenol aldehyde product present, the mol ratio offormaldehyde to substituted phenol, specific type and amount ofmethylolation catalyst, conditions and reactants used to substitute thephenol, methylolation temperature, degree of advancement, and the like.

When such a dehydrated liquid resole is further dehydrated to a watercontent under about 2 weight percent, there is produced a solid,so-called one-stage lump resin, which consists substantially of pureresin, following such dehydration, and, typically, cooling, this solidresin can be broken up or ground into a solid resin having a convenientparticle size range. Since this one-stage lump resin is heat reactive byitself, it is convenient and preferred to cool it during and towards theend of dehydration so as to slow reaction with itself and therebyprevent gelation. This material is characteristically a dark solid,having a softening point somewhere in the range of from about 25 C. to100 C. or even higher.

After such dehydration, the resulting resole resin is then dissolved ina relatively volatile, inert organic solvent medium having properties asdefined above. While the organic liquid used has properties as indicatedabove, it will be appreciated that such liquid can comprise mixtures ofdifferent organic liquids. Preferred liquids are lower alkanols (such asethanol and methanol) and lower alkanones (such as acetone or methylethyl ketone). The term lower refers to less than 7 carbon atoms permolecule as used herein. Aromatic and aliphatic (includingcycloaliphatic) hydrocarbons can also be employed :as solvents for agiven resin, including benzene, toluene, xylene, naphthalene, nonane,octane, petroleum fractions, etc. Preferably, the total Water content ofa varnish of the invention is below about 10 weight percent, and morepreferably falls in the range of from about 0.5 to Weight percent.

Those skilled in the art will appreciate that care should preferably betaken to use an organic liquid system in which the phenolic resoleresins are completely soluble as well as any water present. Adding, forexample, a ketone or an ether-ester solvent like butyl Cellosolve willgenerally improve the water tolerance (ability to dissolve water) of asolvent system.

These varnishes are characteristically dark colored, one-phase, clearliquid solutions, each having a viscosity ranging from about 5 to 5000centipoises. The exact viscosity of a given varnish depends upon manychemical process and product variables. For impregnating applications,viscosities of from about 50 to 500 centipoises are preferred.

The total solids content of a given varnish product can be as high asabout 85 weight percent or even higher, and as low as about 20 weightpercent or even lower, but

preferred solids contents usually fall in the range of from about 25 to65 Weight percent. As those skilled in the art will appreciate, thevarnishes of this invention can be advanced (e.g. cross-linked as byheating to produce larger molecules) to a greater extent without formingprecipitates from the organic solvent phase than is the case ofcorresponding aqueous resole products.

When used for impregnation and reinforcing purposes, the varnishescomprising the resole resins of this invention are useful forimpregnating cellulosic paper, asbestos paper, and other non-woven sheetstructures as well as woven fabrics (cotton, glass fibers, nylon, etc.),etc. Impregnation can be accomplished by any convenient means, includingdipping, coating, spraying, mixing, or the like. The so-impregnatedmaterial is dried to lower the volatiles content and then heated toadvance the resin to the proper degree for the intended use. The resolevarnishes of this invention are useful in the preparation of laminates,such as those made from such impregnated sheet materials. Such laminatesare used in electrical applications as supports or as insulation forconductive elements The laminates are generally manufactured in a sheetor block form which is then punched or otherwise machined to providedesired configuration for a particular end use.

The varnishes comprising resole resins of this invention are also usefulin the manufacture of cloth laminates, and automotive oil filters. Asuitable oil filter media, for example, is prepared by impregnating witha varnish of this invention, cellulosic fiber paper modified with asynthetic fiber (polyester, or the like) and having a thickness of fromabout 5 to 20 mils. Sufiicient of the varnish of a resole resin of thisinvention is used to obtain an impregnated sheet member having a curedresin content of about 15 to 25 percent, based on the weight of thepaper. After such paper is so impregnated, it is heated to advance theresin to a so-called B-stage, and then is corrugated or pleated to fromthe filter element. The filter element is then assembled with the enduse filter container and heated to 250 F. to 350 F. for from 5 to 20minutes to cure the resin. When cured, the product has good flexibilityand low tendency to crack during use.

In general, a varnish of the resole resin of the present invention canbe used to make reinforced plastics. Preferably an organic solution orvarnish containing from about 55 to 65 weight percent (total solutionbasis) of the dissolved phenolic resin is used. In such a preferredsolution, there are from about 2 to 12 parts of dissolved water (totalsolution basis). Solids are conveniently measured using the ASTM TestProcedure D-115-55.

Also a preferred embodiment, the substituted phenol used in makingphenolic resin is made using a carbocyclic compound mixture in whichthere are from about 20 through 40 weight percent of compounds havingthe indene nucleus (as above described), from about 15 through 30 weightpercent of compounds having the dicyclopentadiene nucleus (as abovedescribed) and from about 30 through 65 weight percent of compoundshaving a phenyl group and a vinylidene group (as above described), thepercentage of divinyl benzene in such preferred carbocyclic compoundmixture being as described above, and there being a total of weightpercent of these three components in a given such carbocyclic compoundmixture when such is in a form substantially free of other materials.

The term vinylidene as used herein has generic reference both tovinylidene radicals (CH =C and vinyl radicals (CH =CH or CH=CH-);observe that in carbocyclic compound mixtures used in this inventionhaving a phenyl group substituted by a vinylidene group, alphamethylsubstitution is included in this definition, as well as styrene, methylstyrene, and ethyl styrene.

When dehydrating a resole resin made from a substituted phenol asdescribed above and formaldehyde, convenient reduced pressures rangefrom about 5 to 10 p.s.i.a. to an end temperature of about 60 to 90 C.though those skilled in the art will appreciate that lower and highersuch pressures and temperatures can be used without departing from thespirit and scope of this invention.

EMBODIMENTS The following additional examples are set forth toillustrate more clearly the principles and practices of this inventionto one skilled in the art, and they are not intended to be restrictivebut merely to be illustrative of the invention herein contained. Unlessotherwise stated herein, all parts and percentages are on a weightbasis.

EXAMPLE 1 Charge 100 parts of phenol and 1 part of concentratedsulphuric acid to a suitable reaction vessel and heat the mixture to 50C. Add 70 parts of a carbocyclic compound mixture available commerciallyunder the trade designation Resin Oil from Monsanto Company, having acomposition as given above to the starting mixture while keeping thetemperature stable at 50 C. Hold the temperature of the mixture at 50 C.after addition of such carbocyclic compound mixture for 1 hour and thenadd 7.5 cc. of 28 percent NH OH thereto to neutralize the acid catalyst.To the neutralized reaction mixture, add 2 parts of triethylamine and 60parts of 50 percent formalin (50-50 formaldehyde-water). Now heat thereaction mixture to a reflux at 100 C. and continue refluxing for 4hours. Then recover the resin product by cooling the reaction mixtureand removing volatile material under a vacuum of 28 inches of mercuryuntil the temperature of the mixture rises to 80 C.

EXAMPLE 2 Add 50 parts of methanol and 10 parts of acetone to the resoleresin of Example 1 to form a solution having 71.5 percent solids(measured by heating 1 /2 grams of resin for 3 hours at 135 C.), anOstwald viscosity of 4582 centipoises at 25 C., a pH of 8.42 and a watercontent of 1.76 pecent.

EXAMPLE 3 Charge 100 parts of phenol and 0.1 part of BF to a suitablereaction vessel and heat the mixture to 50 C. Add 30 parts of thecarbocyclic compound mixture used in Example 1 to the mixture graduallyover a period of 30 minutes. Hold the temperature of the mixture at 50C. after addition of the carbocyclic compound mixture for 1 hour andthen add 7.5 parts of 28 percent NH OH to neutralize the acid catalyst.Then add 2 parts of triethylamine and 60 parts of 50 percent formalin tothe neutralized mixture. Now heat the reaction mixture to a reflux at100 C. and continue refluxing for 2 hours. Recover the resin product bycooling the mixture and removing volatile material (mainly water) undera vacuum of 28 inches of mercury until the temperature of the mixturerises to 80 C.

EXAMPLE 4 Add 50 parts of methanol to the resin of Example 3 to form asolution having a solids content of 68.5 percent and a pH of 8.62.

EXAMPLE 5 Charge 100 parts of phenol and 1 part of concentratedsulphuric acid to a suitable reaction vessel. Add 50 parts of thecarbocyclic compound mixture used in Example 1 to the mixture graduallyover a period of 30 minutes. The temperature of the reaction mixturerises due to the exothermic reaction. Hold the temperature of thereaction mixture at 75 C. for 30 minutes and then add 7.5 parts of 28percent NH OH to neutralize the acid catalyst. Then add 2 parts oftriethylamine and 60 parts of 50 percent formalin to the neutralizedmixture. Now heat the mixture to a reflux at 100 C. and continue heatingthe mixture for 2 hours. Recover the resin product by cooling themixture and removing volatile material under a vacuum of 28 inches ofmercury until the temperature of the mixture rises to C.

EXAMPLE 6 Add 60 parts of methanol to the resin of Example 5 to form asolution having a solids content of 68.5 percent and a pH of 8.62.

EXAMPLE 7 A test laminate is prepared from the resin solution of Example2 and 10 mil electrical grade cotton linters paper which has beenpre-impregnated to a 15 percent resin content with a low molecularweight liquid phenolformaldehyde resin. This resin is made as follows:Phenol parts), 50 percent formalin (111 parts) and triethylamine (5parts) is charged to a vessel. After reacting at 70 C. until themixtures free formaldehyde content is less than 4 percent, the mixtureis cooled. About 55 percent solids is obtained.

Eight plies of the so-pre-impregnated paper are then impregnated to atotal resin content of 62 percent with the resin solution of Example 1.The impregnated papers are dried for 19 minutes at C. The 8 plies ofdried impregnated paper are assembled into a deck and cured for 30minutes at 160 C. under a pressure of 1000 p.s.i. to form a laminateabout 4 inch thick.

Various properties of the laminates along with, for comparison purposes,the National Electrical Manufacturers Association (NEMA) specificationsthereof for XXXP type laminates are given below in Table HI.

TABLE III NEMA XXXP Laminate Water absorption, percent 1. 0 0.33Dielectric constant (ASTM D-l50-54T) at- 10 cps., A 4. 6 4. 25 10 cps.,D 24/23 4.8 4. 34 Dissipation factor (ASTM D-54T) at- 10 cps., A .035031 10 eps., D 24/23 035 032 The electrical properties of the resins ofthis invention are well below the maximum NEMA specifications for XXXPtype laminates.

EXAMPLES 8 THROUGH 34 TABLE IV carbocyclic com- Post Catalyst poundmixture 1 reaction Temperatime, Type Amount Type Amount ture, 0. minutes'lhe numbers listed under Type Catalyst designate specificFriedel-Oraits catalysts as fOllOWs-1=Hz$q; 2=BF3 diethyl ether;3=p-toluene sulfonic acid; 4=A1Cl The letters listed under TypeCarbocylic Mixture each designate a specific carbocylic composition asfollows:

N 0TE.Tl1e columns designated, respectively, Phenol, Amount CarbocyclicCompound Mixture, and "Amount Catalyst" are in terms of parts by weight.

EXAMPLE 35 Charge 100 parts of phenol and 0.3 part of concentratedsulphuric acid to a suitable reaction vessel and heat the mixture to 70C. Add 70 parts of carbocyclic compound mixture used in Example 1 to themixture over a period of 45 minutes while keeping the temperature at70-80" C. Hold the temperature of the mixture at 70-80 C. after additionof the carbocyclic compound mixture for minutes. Then add 3 parts ofhexamethylene tetramine, 2 parts of triethylamine and 60 parts of 50%formalin (5050 formaldehyde-water) to the reaction mixture. Now heat thereaction mixture to atmospheric reflux at 100 C. and continue refluxingfor 2.5 hours. Then recover the resole resin product by cooling andremoving volatile material under a vacuum of 25.5 inches of mercuryuntil the temperature of the mixture reaches 60 C.

EXAMPLE 3 6 Add 87 parts of methanol to the resin product of Example 35to form a solution having 59.3% solids (measured by heating 1.5 grams ofresin for 3 hours at 135 C.) and an Ostwald viscosity of 137 centipoisesat C.

EXAMPLE 37 Charge 100 parts of phenol and 1 part of concentratedsulphuric acid to a suitable reaction vessel and heat the mixture to 50C. Add 50 parts of carbocyclic compound mixture used in Example 1 to themixture over a period of minutes while keeping the temperature stable at50 C. After addition of the carbocyclic compound mixture, add 7.5 cc. of28% NH OH to neutralize the acid catalyst. To the neutralized reactionmixture add 2 parts of triethylamine and 60 parts of 50% formalin -(5050formaldehyde-water). Now heat the reaction mixture to a reflux at 100 C.and continue refluxing for 1 /2 hours. Then recover the resole resinproduct by cooling the reaction mixture and removing volatile materialunder a vacuum of 28 inches of mercury until a temperature of C. isreached.

EXAMPLE 38 Add 50 parts of methanol to the reaction product of Example37.

EXAMPLE 39 Charge parts of phenol and 1 part of concentrated sulphuricacid to a suitable reaction vessel and heat the mixture to 50 C. Add 70parts of carbocyclic compound mixture used in Example 1 to the mixtureover a period of 30 minutes while keeping the temperature stable at 50C. After addition of the carbocyclic compound mixture, add 7.5 cc. of28% NH OH thereto to neutralize the acid catalyst. To the neutralizedreaction mixture add 2 parts of triethylamine and 60 parts of 50%formalin (SO-50 formaldehyde-water). Now heat the reaction mixture to areflux at 100 C. and continue refluxing for 2 hours. Recover the resoleresin product by cooling the reaction mixture and removing volatilematerial under a vacuum of 27 inches of mercury until a temperature of80 C. is reached.

EXAMPLE 40 Add 50 parts of methanol to the reaction product of Example39.

EXAMPLE 41 Part A Four test laminates are prepared from the resinsolutions of Examples 2, 36, 38 and 40 and 10 mil electrical grade cotonlinters papers which has been pre-impregnated to a 15% resin contentwith a commercially-available, low molecular weight liquidphenol-formaldehyde resin.

Each laminate is prepared by impregnating 8 plies of the pre-impregnatedpaper to a total resin content of about 60% with one of the resinsolutions of Examples 2, 36, 38 and 40. The impregnated papers are driedat 135 C. until proper laminating flow is attained. The 8 plies of driedimpregnated paper are assembled and cured for 30 minutes to 160 C. undera pressure of 1000 p.s.i. to form a laminate about ,1 inch thick.

Part B Part A is repeated except that an electrical grade phenolic resinmodified with cresol is used.

Part C Part A is repeated except that an unmodified phenolformaldehyderesin prepared by heating 100 parts of phenol in the presence of 1 partBF at 50 C. for 1.5 hours and then adding 60 parts of 50% formalin inthe presence of 7.5 cc. of 28% NH OH and 2 parts of triethylamine underreflux at 100 C. for 20 minutes, is employed in place of the commercialelectrical grade cresolbased resin.

Various properties of the test laminates prepared above along with theNational Electrical Manufacturers Association specification for XXXPlaminates, are given in Table V.

TABLE VI resin Green Number content, tensile of 180 percent strength,flexes to Resin volatiles lbs. /in. rupture 2 Example 42 20.3/8.5 19.0190 t IBIhte force required to break 1" wide strips of the impregnatedpaper, a -s age.

1 After 2 hours conditioning in 300 F. 011.

EXAMPLE 45 Charge 100 parts of phenol and 0.3 part concentrated sulfuricacid to a suitable reaction vessel and heat to 70 C. Add 70 parts ofcarbocyclic compound mixture used in Example 1 to the mixture over aperiod of 45 minutes while keeping the temperature at 7080 C. Hold thetemperature of the mixture at 7080 C. After addition of the carbocycliccompound mixture for 15 minutes; then, add 2 parts of diethanolamine and3 parts ethanolamine and 60 parts of 50 percent formalin to the reactionmixture. Now heat the reaction mixture to atmospheric reflux at 100 C.and continue the refluxing for 1.5 hours. Recover the resole resinproduct by cooling and TABLE V Percent Dielectric Dissipation InsulationWater constant 1 factor 1 resistance 1 absorp- Laminate tion A D24/23 AD24/23 A c96/35/90 Part A:

Ex. 1 resin- 0. 33 4. 25 4. 34 031 032 1 2X10 1. 1X10 Ex. 35 resin. 0.32 4. 71 4. 75 031 031 4. 9X10 2. 7X10 Ex. 37 resin- 0. 42 4. 5 4. 6 033034 8. 6X10 4. 9X10 x. 39 resin. 0. 59 4. 35 4. 4 032 033 1 8X10 1. 3X10Part B 0. 43 4. 70 4. 91 040 042 6. 9X10 2. 2X10 Part C 1. 34 5. 4 5. 9046 051 1. 3X10 1. 4X10 NEM XXXP 1. 00 4. 6 4. 8 035 035 l ASTM TestD-150-54T.

The above data show improvements in electrical properties of modifiedphenolic resins made in accordance with this invention over those of acresol modified electrical grade phenolic resin or a standardphenol-based resin. Furthermore, the electrical properties of the resinsof this invention are well below the maximum NEMA specifications forXXXP type laminates.

EXAMPLE 42 Charge 100 parts of phenol and 0.3 part concentrated sulfuricacid to a suitable reaction vessel and heat to 70 C. Add 70 parts ofcarbocyclic compound mixture used in Example 1 to the mixture over aperiod of minutes while keeping the temperature at 7 0-80 C. Hold thetemperature of the mixture at 70-80 C. after addition of the carbocycliccompound mixture for 15 minutes; then add 3 parts ofhexamethylenetetramine, 2 parts of triethylamine and 60 parts offormalin to the reaction mixturefl Now heat the reaction mixture toatmospheric reflux at 100 C. and continue the refluxing for 1.5 hours.Recover the resole resin product by cooling the reaction mixture andremoving volatile material under a vacuum of mercury until thetemperature of the mixture reaches C.

EXAMPLE 43 Add 92/8 mixture of ethanol/toluene to the resole resinproduct of Example 42 to form a solution having 66% solids.

EXAMPLE 44 Two sheets of cellulose fiber paper containing 12% of asynthetic fiber (polyester) and having a thickness of 10 mils areseparately impregnated with the varnish of removing volatile materialunder a vacuum of mercury until the temperature of the mixture reaches60 C.

EXAMPLE 47 Add a 92/ 8 mixture of ethanol/toluene to the reactionproduct of Example 45 to form a solution having 66 percent solids.

In the foregoing examples whenever a liquid aqueous resole resin is madefrom a substituted phenol and aldehyde in accordance with the teachingsof this invention there is produced first an aqueous emulsion containingwater and methylolated substituted phenol plus some advancedmethylolated materials. When this material is dehydrated by heatingunder vacuum (the temperature being about 60 to C. and the vacuumpressure being about 22 to 28 mm. Hg) there is produced when the residuecontains less than about 20 weight percent of water a high solid,viscous, dark colored, single phase fluid which is one of the resoleproducts of this invention.

When this fluid is further dehydrated under similar conditions with awater content of about 2 weight percent, there is produced a solidone-stage lump resin.

When the afore-indicated emulsion is dehydrated under theafore-indicated heat and temperature reduced pressures, thephenol-aldehyde resin is first reduced to a water content under about 20weight percent and is thereafter dissolved in, respectively, methanoland ethanol to produce resole varnishes from the resole resins of thisinvention.

What is claimed is:

1. A resole resin comprising the product of formaldehyde and asubstituted phenol mixture in a mol ratio of 0.8:1 to 2:1 reacted in thepresence of a basic catalyst, said substituted phenol mixture havingbeen prepared by alkylation of phenol with a mixture of carbocycliccompounds under acid conditions at a temperature in the range of 25 to200 C. whereby 10 to 80 parts by weight of the mixture of carbocycliccompounds reacts with 100 parts by weight of phenol, said mixture ofcarbocyclic compounds comprising:

(A) from 10 to 40 parts by weight of compounds each molecule of whichhas:

(1) the indene nucleus,

(2) from 9 to 13 carbon atoms,

(3) as nuclear substituents from O to 4 methyl (B) from 5 to 70 parts byweight of compounds each molecule of which has:

(1) the dicyclopentadiene nucleus,

(2) from 10 to 13 carbon atoms,

(3) as nuclear substituents from to 3 methyl groups;

(C) from 15 to 65 parts by weight of compounds each molecule of whichhas:

(1) a phenyl group substituted by a vinylidene (2) from 8 to 13 carbonatoms,

(3) as substituents from 0 to 3 groups selected from the classconsisting of methyl and ethyl; and

(D) from 0 to parts by Weight of divinyl benzene. 2. The resole resin ofclaim 1, wherein said carbocyclic compound mixture comprises:

(A) from 20 to 40 parts by weight of compounds each molecule of whichhas:

(1) the indene nucleus,

(2) from 9 to 13 carbon atoms,

(3) as nuclear substituents from 0 to 4 methyl groups;

(B) from 15 to 30 parts by weight of compounds each molecule of whichhas:

(1) the dicyclopentadiene nucleus,

(2) from 10 to 13 carbon atoms,

(3) as nuclear substituents from 0 to 3 methyl groups;

(C) from 30 to parts by weight of compounds each molecule of which has:

(1) a phenyl group substituted by a vinylidene (2) from 8 to 13 carbonatoms,

(3) as substituents from 0 to 3 groups selected from the classconsisting of methyl and ethyl; and

(D) from 0 to 5 parts by weight of divinyl benzene.

3. The resole resin of claim 1, wherein the basic catalyst is selectedfrom the group consisting of the lower primary, secondary and tertiaryamines of molecular weight below 300.

4. The resole resin of claim 1, wherein the basic catalyst is selectedfrom the group consisting of ammonium hydroxide, hexamethylene tetramineand triethylamine.

5. The resole resin of claim 1 made from the reaction product of between15 and 55 parts by weight of carbocyclic compound and parts by weight ofphenol.

6. The resole resin of claim 1, wherein the mixture of carbocycliccompounds has a boiling range from 280 F. to 420 F.

References Cited UNITED STATES PATENTS HOWARD E. SCHAIN, PrimaryExaminer US. Cl. X.R. 26029.3

